Diorganylphosphinic acid salts, method for the production thereof and the use thereof

Abstract

The invention relates to diorganylphosphinic salts containing 0.0001% to 99.9999% by weight of iron, to a process for preparation thereof and to the use thereof.

The invention claimed is: 
     
       1. A diorganylphosphinic salt conforming to formula (II) 
       
         
           
           
               
               
           
         
         wherein the C a H 2a+1  and C b H 2b+1  groups are the same or different and are each methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl,
 y is 0.00001 to 0.091, 
 m is 1 to 4, 
 n is 2 to 3, 
 M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and/or K, and 
 M′ is Fe. 
 
       
     
     
       2. The diorganylphosphinic salt as claimed in  claim 1 , wherein the iron is in the form of iron(II) dialkylphosphinates and/or iron(III) dialkylphosphinates. 
     
     
       3. The diorganylphosphinic salt as claimed in  claim 1 , wherein M and M′ are in the form of a homogeneous ionic compound with the (C a H 2a+1 )(C b H 2b+1 )PO 2  anions. 
     
     
       4. The diorganylphosphinic salt as claimed in  claim 1 , which further comprises telomer ions, where the telomer ions are those of the empirical formula (VI)
   H—(C w H 2w ) k P(O)(O (−) )(C x H 2x ) l —H  (VI)
 
 where, in formula (VI), independently of one another,
 k is 1 to 9, l is 1 to 9, w is 2 to 9, and x is 2 to 9. 
 
 
     
     
       5. The diorganylphosphinic salt as claimed in  claim 4 , wherein, in formula (VI),
 w and x are each 2 to 4 and k and l are each 1 to 4. 
 
     
     
       6. The diorganylphosphinic salt as claimed in  claim 4 , wherein, in formula (VI),
 w and x are each 2 or 3 and k and l are each 1 to 3. 
 
     
     
       7. The diorganylphosphinic salt as claimed in  claim 4 , which comprises
 a) 60 to 99.8999 P % dialkylphosphinic salts of the formula (II), and 
 b) 0.1 to 40 P % of telomer ions of the formula (VI), 
 
       where the sum total of a) and b) is 100 P %, with the proviso that the diorganylphosphinic salts of the formula (II) and the telomer ions of the formula (VI) are each different compounds. 
     
     
       8. The diorganylphosphinic salt as claimed in  claim 4 , wherein the ions M, M′, (C a H 2a+1 )(C b H 2b+1 )PO 2   − , H—(C w H 2w ) k PO 2   − (C x H 2x ) l —H and anions of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid, ethyloctylphosphinic acid, sec-butylethylphosphinic acid, 1-ethylbutyl(butyl)phosphinic acid, ethyl(1-methylpentyl)phosphinic acid, di-sec-butylphosphinic acid (di(1-methylpropyl)phosphinic acid), propyl(hexyl)phosphinic acid, dihexylphosphinic acid, hexyl(nonyl)phosphinic acid, propyl(nonyl)phosphinic acid, dinonylphosphinic acid, dipropylphosphinic acid, butyl(octyl)phosphinic acid, hexyl(octyl)phosphinic acid, dioctylphosphinic acid, ethyl(cyclopentylethyl)phosphinic acid, butyl(cyclopentylethyl)phosphinic acid, ethyl(cyclohexylethyl)phosphinic acid, butyl(cyclohexylethyl)phosphinic acid, ethyl(phenylethyl)phosphinic acid, butyl(phenylethyl)phosphinic acid, ethyl(4-methylphenylethyl)phosphinic acid, butyl(4-methylphenylethyl)phosphinic acid, butylcyclopentylphosphinic acid, butylcyclohexylethylphosphinic acid, butylphenylphosphinic acid, ethyl(4-methylphenyl)phosphinic acid and/or butyl(4-methylphenyl)phosphinic acid together constitute a homogeneous ionic compound. 
     
     
       9. The diorganylphosphinic salt as claimed in  claim 4 , wherein the telomer ions are in the form of their metal salts, these being metal salts of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid, ethyloctylphosphinic acid, sec-butylethylphosphinic acid, 1-ethylbutyl(butyl)phosphinic acid, ethyl(1-methylpentyl)phosphinic acid, di-sec-butylphosphinic acid (di-1-methylpropylphosphinic acid), propyl(hexyl)phosphinic acid, dihexylphosphinic acid, hexyl(nonyl)phosphinic acid, propyl(nonyl)phosphinic acid, dinonylphosphinic acid, dipropylphosphinic acid, butyl(octyl)phosphinic acid, hexyl(octyl)phosphinic acid, dioctylphosphinic acid, ethyl(cyclopentylethyl)phosphinic acid, butyl(cyclopentylethyl)phosphinic acid, ethyl(cyclohexylethyl)phosphinic acid, butyl(cyclohexylethyl)phosphinic acid, ethyl(phenylethyl)phosphinic acid, butyl(phenylethyl)phosphinic acid, ethyl(4-methylphenylethyl)phosphinic acid, butyl(4-methylphenylethyl)phosphinic acid, butylcyclopentylphosphinic acid, butylcyclohexylethylphosphinic acid, butylphenylphosphinic acid, ethyl(4-methylphenyl)phosphinic acid and/or butyl(4-methylphenyl)phosphinic acid, and the metal of the metal salt comes from the group of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and/or K. 
     
     
       10. The diorganylphosphinic salt as claimed in  claim 1 , which has
 a particle size of 0.1 to 1000 μm, 
 a bulk density of 80 to 800 g/L, 
 a tamped density of 100 g/L to 1100 g/L, 
 an angle of repose of 5 to 45 degrees, 
 a BET surface area of 1 to 40 m 2 /g, 
 L color values of 85 to 99.9, 
 a color values of −4 to +9, and 
 b color values of −2 to +6. 
 
     
     
       11. The diorganylphosphinic salt as claimed in  claim 1 , which has
 a particle size of 0.5 to 800 μm, 
 a bulk density of 80 to 600 g/L, 
 a tamped density of 600 g/L to 800 g/L, and 
 an angle of repose of 10 to 40 degrees. 
 
     
     
       12. A process for producing diorganylphosphinic salts as claimed in  claim 1 , which comprises
 a) in a process stage 1 adding 0.9 to 1.1 molecules of olefin per P onto a water-soluble salt of the hypophosphorous acid or the acid itself, 
 b) in a process stage 2 adding 0.9 to 1.1 additional molecules of olefin per P onto the intermediate from a) to give dialkylphosphinic acid or salt thereof, 
 c) in a process stage 3 adding one to 9 further olefin molecules onto 0% to 20% of the dialkylphosphinate molecules from process stage 1, so as to form telomers, and 
 d) in a process stage 4 conducting a crystallization of the intermediate from b) or c) with a metal salt and an iron salt. 
 
     
     
       13. A process for producing diorganylphosphinic salts as claimed in  claim 1 , which comprises
 a) in a process stage 1 adding 0.9 to 1.1 molecules of olefin per P onto a water-soluble salt of the hypophosphorous acid or the acid itself, 
 b) in a process stage 2 adding 0.9 to 1.1 additional molecules of olefin per P onto the intermediate from a) to give dialkylphosphinic acid or salt thereof, 
 c) in a process stage 3 adding one to 9 further olefin molecules onto 0% to 20% of the dialkylphosphinate molecules from process stage 1, so as to form telomers, 
 d) in a process stage 4 conducting a crystallization with a metal salt and/or an iron salt, and 
 e) in a process stage 5 conducting a coprecipitation of the intermediate from d) with a metal salt or an iron salt. 
 
     
     
       14. A process for producing diorganylphosphinic salts as claimed in  claim 1 , which comprises
 a) in a process stage 1 adding 0.9 to 1.1 molecules of olefin per P onto a water-soluble salt of the hypophosphorous acid or the acid itself, 
 b) in a process stage 2 adding 0.9 to 1.1 additional molecules of olefin per P onto the intermediate from a) to give dialkylphosphinic acid or salt thereof, 
 c) in a process stage 3 conducting a crystallization with a metal salt and/or an iron salt, and 
 d) then in a process stage 4 physically mixing the telomers. 
 
     
     
       15. The process as claimed in  claim 12 , wherein the iron salts are fluorides, chlorides, bromides, iodides, iodate, perchlorate, oxides, hydroxides, peroxides, superoxides, sulfates, hydrogensulfates, sulfate hydrates, sulfites, peroxosulfates, nitrides, phosphides, nitrates, nitrate hydrates, nitrites, phosphates, peroxophosphates, phosphites, hypophosphites, pyrophosphates, carbonates, hydrogencarbonates, hydroxide carbonates, carbonate hydrates, silicates, hexafluorosilicates, hexafluorosilicate hydrates, stannates, borates, polyborates, peroxoborates, thiocyanates, cyanates, cyanides, chromates, chromites, molybdates, permanganates, formates, acetates, acetate hydrates, trifluoroacetate hydrates, propionates, butyrates, valerates, caprylates, oleates, stearates, oxalates, tartrates, citrates, basic citrates, citrate hydrates, benzoates, salicylates, lactates, lactate hydrates, acrylates, maleates, salts of succinic acid, salts of glycine, phenoxides, para-phenolsulfonates, para-phenolsulfonate hydrates, acetylacetonate hydrates, tannates, dimethyldithiocarbamates, trifluoromethanesulfonate, alkylsulfonates and/or aralkylsulfonates. 
     
     
       16. The process as claimed in  claim 12 , wherein the metal of the metal salt comes from the group of Al, Te, Fe and/or Zn. 
     
     
       17. A flame retardant comprising a diorganylphosphinic salt as claimed in  claim 1 . 
     
     
       18. The diorganylphosphinic salts as claimed in  claim 1  together with synergists, where the synergists are melamine phosphate, dimelamine phosphate, pentamelamine triphosphate, trimelamine diphosphate, tetrakismelamine triphosphate, hexakismelamine pentaphosphate, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphates, melam polyphosphates, melem polyphosphates and/or melon polyphosphates; or melamine condensation products such as melam, melem and/or melon; or oligomeric esters of tris(hydroxyethyl) isocyanurate with aromatic polycarboxylic acids, benzoguanamine, tris(hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine, melamine cyanurate, urea cyanurate, dicyandiamide and/or guanidine; or nitrogen-containing phosphates of the formula (NH 4 ) y H 3-y PO 4  or (NH 4 PO 3 ) z  with y=1 to 3 and z=1 to 10 000; or aluminum phosphites, aluminum pyrophosphites, aluminum phosphonates, aluminum pyrophosphonates; or silicates, zeolites, silicas, ceramic powder, zinc compounds, zinc borate, zinc carbonate, zinc stannate, zinc hydroxystannate, zinc phosphate, zinc sulfide, zinc oxide, zinc hydroxide, tin oxide hydrate, basic zinc silicate, zinc molybdate, magnesium hydroxide, hydrotalcite, magnesium carbonate, calcium magnesium carbonate; or salts of ethylphosphonic acid, of propylphosphonic acid, of butylphosphonic acid, of n-butylphosphonic acid, of sec-butylphosphonic acid, of hexylphosphonic acid and/or of octylphosphonic acid. 
     
     
       19. The flame retardant as claimed in  claim 17 , further comprising antioxidants, UV stabilizers, gamma ray stabilizers, hydrolysis stabilizers, antistats, emulsifiers, nucleating agents, plasticizers, processing auxiliaries, impact modifiers, dyes, and/or pigments. 
     
     
       20. A flame retardant comprising 0.0001% to 99.7999% by weight of diorganylphosphinic salts as claimed in  claim 1 , 0.1% to 40% by weight of synergists and 0.1% to 40% by weight of additives, where the sum of the components is 100% by weight. 
     
     
       21. A flame-retardant thermoplastic or thermoset polymer molding composition or polymer molding, film, filament and/or fiber comprising 0.5% to 45% by weight of diorganylphosphinic salts as claimed in  claim 1 , 0.5% to 95% by weight of thermoplastic or thermoset polymer or mixtures thereof, 0% to 55% by weight of additives and 0% to 55% by weight of filler or reinforcing materials, where the sum of the components is 100% by weight. 
     
     
       22. The thermoplastic or thermoset polymer molding composition, polymer molding, film, filament and/or fiber as claimed in  claim 21 , wherein the polymer comprises thermoplastic polymers of the HI (high-impact) polystyrene, polyphenylene ether, polyamide, polyester or polycarbonate type, and blends or polymer blends of the ABS (acrylonitrile-butadiene-styrene) or PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) or PPE/HIPS (polyphenylene ether/HI polystyrene) polymer, and/or thermoset polymers of unsaturated polyester or epoxy resins.